CN102775943A - Acrylate pressure-sensitive adhesive containing crystalline polyester and preparation method thereof - Google Patents
Acrylate pressure-sensitive adhesive containing crystalline polyester and preparation method thereof Download PDFInfo
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- CN102775943A CN102775943A CN2012102777133A CN201210277713A CN102775943A CN 102775943 A CN102775943 A CN 102775943A CN 2012102777133 A CN2012102777133 A CN 2012102777133A CN 201210277713 A CN201210277713 A CN 201210277713A CN 102775943 A CN102775943 A CN 102775943A
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Abstract
The invention provides an acrylate pressure-sensitive adhesive containing crystalline polyester and a preparation method of the acrylate pressure-sensitive adhesive. Particularly, the acrylate pressure-sensitive adhesive containing crystalline polyester is prepared from crystalline unsaturated polyester and an acrylate pressure-sensitive adhesive through graft polymerization. The acrylate pressure-sensitive adhesive containing crystalline polyester has the characteristics of regular structure, large cohesion, strong cohesive strength and the like, so that the acrylate pressure-sensitive adhesive containing crystalline polyester has excellent application effect and wider application prospect.
Description
Technical field
The present invention relates to a kind of acrylate pressure-sensitive adhesive that contains the crystal type polyester and preparation method thereof, particularly relate to a kind of acrylate pressure-sensitive adhesive that contains the crystal type polyester that obtains by crystal type unsaturated polyester and acrylate pressure sensitive adhesive, through graft polymerization and preparation method thereof.
Background technology
Pressure sensitive adhesive is to presser sensor, need heat, not need big pressure, only need refer to that the power that presses just can realize bonding a kind of sizing agent.Be characterized in gluing that easily that takes off is not difficult, stripping and not decreasing can not dried up at long time inner glue layer, so pressure sensitive adhesive is also referred to as non-setting adhesive.
We see KT plate foaming phenomenon through regular meeting in the life; Its reason is: be attached to the gum on the KT plate, its part acrylic ester pressure-sensitive contains residual solvent toluene etc., and the toluene equal solvent can have solvation to the HIPS surface layer of KT plate; After these residual solvents pass surface layer; The foam wall of PS foam central layer is by eating thrown, and plate core the inside has the gas release of certain pressure to come out, and makes the local crowning blister of gum.
In order to solve the blistered problem of KT plate, we need set about from two aspects: the one, and the solvent and the reaction of KT plate that suppress the sizing agent produce bubble; The 2nd, the bonding strength of the sizing agent in the raising gum.
PVC or PP or PE or PET rete that patent CN201201347Y compound again one deck solvent resistance on the HIPS of conventional KT plate rete is more much better than HIPS.Improved the KT plate surface layer corrosive of anti-toluene ability, but can not fundamentally prevent to bubble.Still to consider to improve that the bonding strength of sizing agent prevents bubble problem in the gum.
The cohesive strength that improves acrylate pressure-sensitive adhesive at present mainly contains physics tackify and chemical modification tackify.The patent of physics tackify is a lot, and patent CN1760302A adopts paracril class and vinylformic acid gluing agent physical blending to obtain a kind of sizing agent of high-peeling strength.But because the high solubility parameter of acrylic pressure sensitive adhesives, so the modified adhesive group partition inter-capacitive that obtains is bad.Show as viscosity and descend, stripping strength reduces.The research of chemical modification tackify is more, and patent CN101368073A has introduced a kind of modification solvent acrylate adhesive, and it adopts Acrylic Acid Monomer, modified monomer, function monomer to be polymerized.This sizing agent has stronger cohesive force to leather, metal, bamboo and wood etc.Patent CN101386775A; Introduced a kind of tackiness agent based on polyester-graft-poly (methyl) Yodo Sol GH 28; It has only solved low cost, solvent resistance and the resistance toheat of Hotmelt Adhesive, but its cohesive strength size is general, can not play the effect of pressure sensitive adhesive.
Summary of the invention
The technical problem that the present invention will solve is to improve the bonding strength of acrylate pressure-sensitive adhesive.
In order to solve the technical problem of above-mentioned existence, the present invention takes following technical scheme:
The invention provides a kind of prescription and preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester; Be with crystal type unsaturated polyester and acrylate pressure-sensitive adhesive,, make a kind of acrylate pressure-sensitive adhesive that contains the crystal type polyester through graft copolymerization; It has a certain amount of crystalline structure; Force of cohesion is bigger, so its cohesive strength improves effective control foaming problem greatly.
The composition of raw materials of a kind of crystal type unsaturated polyester that arrives involved in the present invention is as follows:
The massfraction of catalyzer is to be benchmark with the total content of acid in the prescription;
The x of component C must be greater than the x sum of component A and B component;
Component A is a unsaturated acid anhydride, a kind of in MALEIC ANHYDRIDE and the FUMARIC ACID TECH GRADE acid anhydride;
B component is a monounsaturated dicarboxylic acid, a kind of in terephthalic acid and the hexanodioic acid;
Component C is saturated divalent alcohol, a kind of in butyleneglycol, Ucar 35 and the terepthaloyl moietie;
Catalyzer is a kind of in tetrabutyl titanate, Antimony Trioxide: 99.5Min and the dibutyl tin.
The process step and the condition of this kind crystal type unsaturated polyester preparation provided by the invention are following:
Component A, B component, component C and catalyst by proportion are dropped in the reactor drum, heating, dissolving is stirred, and when temperature rises to 180 ℃, feeds N
2, discharge small molecules and water; Be incubated 1.5h then, elevate the temperature 10 ℃ again, be incubated 1.5h once more, reach 220 ℃ until temperature by that analogy; When the material acid number is reduced to 50～100mgKOHg
-1The time, reduce to room temperature, obtain the unsaturated polyester that number-average molecular weight is 1000～2000g/mol, its percent crystallinity is 10%～30%;
The invention provides a kind of acrylate pressure-sensitive adhesive that contains the crystal type polyester, its composition of raw materials is as follows:
Above-mentioned involved massfraction is a benchmark with the raw material gross weight of participating in reaction all;
Component a is a hard monomer, a kind of in vinyl cyanide, acrylic amide, vinylbenzene, TEB 3K and the methyl acrylate;
Components b is a soft monomer, a kind of in Bing Xisuandingzhi, ethyl propenoate and the ethyl acrylate;
Amount of component b is a function monomer, a kind of in vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methylacrylic acid, Rocryl 400 and the Rocryl 410;
Component d is the crystal type unsaturated polyester;
Solvent adopts a kind of in ETHYLE ACETATE and the YLENE;
Initiator adopts Diisopropyl azodicarboxylate.
Above-mentioned involved massfraction is a benchmark with the raw material gross weight of participating in reaction all.
A kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester provided by the present invention is: component a, components b, amount of component b, component d, solvent and initiator are mixed in proportion; Get 1/3～1/2 of mixing solutions and join in the reaction kettle, stir and be heated to 80 ℃, slowly drip remaining mixing solutions then; And in 1～2h, be added dropwise to complete; Continue reaction and finish, reduce temperature then, promptly obtain containing the acrylate pressure-sensitive adhesive of crystal type polyester to room temperature up to reaction;
Beneficial effect:
The present invention obtains a kind of acrylate pressure-sensitive adhesive that contains the crystal type polyester through with crystal type unsaturated polyester and acrylate pressure-sensitive adhesive graft copolymerization, and this acrylate pressure-sensitive adhesive that contains the crystal type polyester has following characteristics:
1, the number-average molecular weight of unsaturated polyester is 1000-2000g/mol.
2, the number-average molecular weight of unsaturated polyester is when 1 described scope; The number of two keys is one to two in the molecular chain; The performance characteristics of the unsaturated polyester of this structure is: suitable degree of unsaturation, both reduced the molecule chain rigidity, and prevented effectively that again the molecule interchain is crosslinked; The more important thing is, for graft copolymerization at the back provides a certain amount of grafting site.
3, the scope of the percent crystallinity of unsaturated polyester is 10%--30%.
4, in order to improve the percent crystallinity of unsaturated polyester, the technology that we take is: polymerization single polymerization monomer is selected butyleneglycol for use.The molecular chain structure that is characterized in butyleneglycol is regular, makes whole molecular chain have certain kindliness after the polymerization, helps the raising of the crystal property of unsaturated polyester, obtains having the unsaturated polyester of certain percent crystallinity.
Advantage of the present invention is: this acrylate pressure-sensitive adhesive that contains the crystal type polyester obtains through crystal type polyester and acrylate pressure-sensitive adhesive graft copolymerization, so it not only has the general characteristic of pressure sensitive adhesive, has also increased its bonding strength greatly.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
A kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester; It is characterized in that: vinyl cyanide, Bing Xisuandingzhi, Hydroxyethyl acrylate, crystal type unsaturated polyester, ETHYLE ACETATE and Diisopropyl azodicarboxylate are mixed in proportion; Get 1/3～1/2 of mixing solutions and join in the reaction kettle, stir and be heated to 80 ℃, slowly drip remaining mixing solutions then; And in 1～2h, be added dropwise to complete; Continue reaction and finish, reduce temperature then, promptly obtain containing the acrylate pressure-sensitive adhesive of crystal type polyester to room temperature up to reaction;
Wherein, composition of raw materials is following:
Above-mentioned involved massfraction is a benchmark with the raw material gross weight of participating in reaction all;
The process step of the preparation of described crystal type unsaturated polyester is following:
MALEIC ANHYDRIDE, terephthalic acid, butyleneglycol and tetrabutyl titanate are dropped in the reactor drum in proportion, heating, dissolving is stirred, and when temperature rises to 180 ℃, feeds N
2, discharge small molecules and water; Be incubated 1.5h then, elevate the temperature 10 ℃ again, be incubated 1.5h once more, reach 220 ℃ until temperature by that analogy; When the material acid number is reduced to 100mgKOHg
-1The time, reduce to room temperature, obtain the unsaturated polyester that number-average molecular weight is 1000g/mol, its percent crystallinity is 30%; Second-order transition temperature is-30 ℃;
The composition of raw materials of preparation crystal type unsaturated polyester is following:
The massfraction of tetrabutyl titanate is to be benchmark with the total content of acid in the prescription.
Embodiment 2
A kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester; It is characterized in that: TEB 3K, Bing Xisuandingzhi, Rocryl 400, crystal type unsaturated polyester, YLENE and Diisopropyl azodicarboxylate are mixed in proportion; Get 1/3～1/2 of mixing solutions and join in the reaction kettle, stir and be heated to 80 ℃, slowly drip remaining mixing solutions then; And in 1～2h, be added dropwise to complete; Continue reaction and finish, reduce temperature then, promptly obtain containing the acrylate pressure-sensitive adhesive of crystal type polyester to room temperature up to reaction;
Wherein, composition of raw materials is following:
Above-mentioned involved massfraction is a benchmark with the raw material gross weight of participating in reaction all;
The process step of the preparation of described crystal type unsaturated polyester is following:
FUMARIC ACID TECH GRADE acid anhydride, hexanodioic acid, Ucar 35 and tetrabutyl titanate are dropped in the reactor drum in proportion, heating, dissolving is stirred, and when temperature rises to 180 ℃, feeds N
2, discharge small molecules and water; Be incubated 1.5h then, elevate the temperature 10 ℃ again, be incubated 1.5h once more, reach 220 ℃ until temperature by that analogy; When the material acid number is reduced to 50mgKOHg
-1The time, reduce to room temperature, obtain the unsaturated polyester that number-average molecular weight is 2000g/mol, its percent crystallinity is 10%; Second-order transition temperature is-10 ℃;
The composition of raw materials of preparation crystal type unsaturated polyester is following:
The massfraction of tetrabutyl titanate is to be benchmark with the total content of acid in the prescription.
Embodiment 3
A kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester; It is characterized in that: acrylic amide, ethyl acrylate, Rocryl 410, crystal type unsaturated polyester, ETHYLE ACETATE and Diisopropyl azodicarboxylate are mixed in proportion; Get 1/3～1/2 of mixing solutions and join in the reaction kettle, stir and be heated to 80 ℃, slowly drip remaining mixing solutions then; And in 1～2h, be added dropwise to complete; Continue reaction and finish, reduce temperature then, promptly obtain containing the acrylate pressure-sensitive adhesive of crystal type polyester to room temperature up to reaction;
Wherein, composition of raw materials is following:
Above-mentioned involved massfraction is a benchmark with the raw material gross weight of participating in reaction all;
The process step of the preparation of described crystal type unsaturated polyester is following:
MALEIC ANHYDRIDE, hexanodioic acid, butyleneglycol and dibutyl tin are dropped in the reactor drum in proportion, heating, dissolving is stirred, and when temperature rises to 180 ℃, feeds N
2, discharge small molecules and water; Be incubated 1.5h then, elevate the temperature 10 ℃ again, be incubated 1.5h once more, reach 220 ℃ until temperature by that analogy; When the material acid number is reduced to 80mgKOHg
-1The time, reduce to room temperature, obtain the unsaturated polyester that number-average molecular weight is 1500g/mol, its percent crystallinity is 20%; Second-order transition temperature is-20 ℃;
The composition of raw materials of preparation crystal type unsaturated polyester is following:
The massfraction of dibutyl tin is to be benchmark with the total content of acid in the prescription.
Embodiment 4
A kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester; It is characterized in that: vinylbenzene, Bing Xisuandingzhi, Propylene glycol monoacrylate, crystal type unsaturated polyester, YLENE and Diisopropyl azodicarboxylate are mixed in proportion; Get 1/3～1/2 of mixing solutions and join in the reaction kettle, stir and be heated to 80 ℃, slowly drip remaining mixing solutions then; And in 1～2h, be added dropwise to complete; Continue reaction and finish, reduce temperature then, promptly obtain containing the acrylate pressure-sensitive adhesive of crystal type polyester to room temperature up to reaction;
Wherein, composition of raw materials is following:
Above-mentioned involved massfraction is a benchmark with the raw material gross weight of participating in reaction all;
The process step of the preparation of described crystal type unsaturated polyester is following:
FUMARIC ACID TECH GRADE acid anhydride, terephthalic acid, butyleneglycol and Antimony Trioxide: 99.5Min are dropped in the reactor drum in proportion, heating, dissolving is stirred, and when temperature rises to 180 ℃, feeds N
2, discharge small molecules and water; Be incubated 1.5h then, elevate the temperature 10 ℃ again, be incubated 1.5h once more, reach 220 ℃ until temperature by that analogy; When the material acid number is reduced to 80mgKOHg
-1The time, reduce to room temperature, obtain the unsaturated polyester that number-average molecular weight is 1500g/mol, its percent crystallinity is 20%; Second-order transition temperature is-18 ℃;
The composition of raw materials of preparation crystal type unsaturated polyester is following:
The massfraction of Antimony Trioxide: 99.5Min is to be benchmark with the total content of acid in the prescription.
Embodiment 5
A kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester; It is characterized in that: methyl acrylate, ethyl acrylate, vinylformic acid, crystal type unsaturated polyester, ETHYLE ACETATE and Diisopropyl azodicarboxylate are mixed in proportion; Get 1/3～1/2 of mixing solutions and join in the reaction kettle, stir and be heated to 80 ℃, slowly drip remaining mixing solutions then; And in 1～2h, be added dropwise to complete; Continue reaction and finish, reduce temperature then, promptly obtain containing the acrylate pressure-sensitive adhesive of crystal type polyester to room temperature up to reaction;
Wherein, composition of raw materials is following:
Above-mentioned involved massfraction is a benchmark with the raw material gross weight of participating in reaction all;
The process step of the preparation of described crystal type unsaturated polyester is following:
MALEIC ANHYDRIDE, terephthalic acid, terepthaloyl moietie and Antimony Trioxide: 99.5Min are dropped in the reactor drum in proportion, heating, dissolving is stirred, and when temperature rises to 180 ℃, feeds N
2, discharge small molecules and water; Be incubated 1.5h then, the 10 ° of C that elevate the temperature again are incubated 1.5h once more, reach 220 ℃ until temperature by that analogy; When the material acid number is reduced to 60mgKOHg
-1The time, reduce to room temperature, obtain the unsaturated polyester that number-average molecular weight is 1700g/mol, its percent crystallinity is 15%; Second-order transition temperature is-20 ℃;
The composition of raw materials of preparation crystal type unsaturated polyester is following:
The massfraction of Antimony Trioxide: 99.5Min is to be benchmark with the total content of acid in the prescription.
Embodiment 6
A kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester; It is characterized in that: TEB 3K, Bing Xisuandingzhi, methylacrylic acid, crystal type unsaturated polyester, YLENE and Diisopropyl azodicarboxylate are mixed in proportion; Get 1/3～1/2 of mixing solutions and join in the reaction kettle, stir and be heated to 80 ℃, slowly drip remaining mixing solutions then; And in 1～2h, be added dropwise to complete; Continue reaction and finish, reduce temperature then, promptly obtain containing the acrylate pressure-sensitive adhesive of crystal type polyester to room temperature up to reaction;
Wherein, composition of raw materials is following:
Above-mentioned involved massfraction is a benchmark with the raw material gross weight of participating in reaction all;
The process step of the preparation of described crystal type unsaturated polyester is following:
MALEIC ANHYDRIDE, Succinic Acid, Ucar 35 and dibutyl tin are dropped in the reactor drum in proportion, heating, dissolving is stirred, and when temperature rises to 180 ℃, feeds N
2, discharge small molecules and water; Be incubated 1.5h then, elevate the temperature 10 ℃ again, be incubated 1.5h once more, reach 220 ℃ until temperature by that analogy; When the material acid number is reduced to 80mgKOHg
-1The time, reduce to room temperature, obtain the unsaturated polyester that number-average molecular weight is 1500g/mol, its percent crystallinity is 25%; Second-order transition temperature is-22 ℃;
The composition of raw materials of preparation crystal type unsaturated polyester is following:
The massfraction of dibutyl tin is to be benchmark with the total content of acid in the prescription.
Claims (9)
1. acrylate pressure-sensitive adhesive that contains the crystal type polyester; It is characterized in that: the described acrylate pressure-sensitive adhesive that contains the crystal type polyester is grafted with the crystal type polyester, and it is 1%～9% that the composition of said crystal type polyester accounts for the said mass percent that contains the acrylate pressure-sensitive adhesive of crystal type polyester; The described second-order transition temperature that contains the acrylate pressure-sensitive adhesive of crystal type polyester is-10 ℃～-30 ℃;
Described crystal type polyester is to be opened and got by two keys of crystal type unsaturated polyester; Contain one to two unsaturated double-bond in the described crystal type unsaturated polyester; The scope of the percent crystallinity of described crystal type unsaturated polyester is 10%～30%, and number-average molecular weight is 1000～2000g/mol.
2. a kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester as claimed in claim 1; It is characterized in that: component a, components b, amount of component b, component d, solvent and initiator are mixed in proportion; Get 1/3～1/2 of mixing solutions and join in the reaction kettle, stir and be heated to 80 ℃, slowly drip remaining mixing solutions then; And in 1～2h, be added dropwise to complete; Continue reaction and finish, reduce temperature then, promptly obtain containing the acrylate pressure-sensitive adhesive of crystal type polyester to room temperature up to reaction;
Wherein, composition of raw materials is following:
Above-mentioned involved massfraction is a benchmark with the raw material gross weight of participating in reaction all;
Described component a is a hard monomer, a kind of in vinyl cyanide, acrylic amide, vinylbenzene, TEB 3K and the methyl acrylate;
Described components b is a soft monomer, a kind of in Bing Xisuandingzhi, ethyl propenoate and the ethyl acrylate;
Described amount of component b is a function monomer, a kind of in vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methylacrylic acid, Rocryl 400 and the Rocryl 410;
Described component d is the crystal type unsaturated polyester;
The process step of the preparation of described crystal type unsaturated polyester is following:
Component A, B component, component C and catalyst by proportion are dropped in the reactor drum, heating, dissolving is stirred, and when temperature rises to 180 ℃, feeds N
2, discharge small molecules and water; Be incubated 1.5h then, elevate the temperature 10 ℃ again, be incubated 1.5h once more, reach 220 ℃ until temperature by that analogy; When the material acid number is reduced to 50～100mgKOHg
-1The time, reduce to room temperature, obtain the unsaturated polyester that number-average molecular weight is 1000～2000g/mol, its percent crystallinity is 10%～30%; The composition of raw materials of preparation crystal type unsaturated polyester is following:
The massfraction of catalyzer is to be benchmark with the total content of acid in the prescription;
The x of component C must be greater than the x sum of component A and B component;
Wherein, component A is a unsaturated acid anhydride, a kind of in MALEIC ANHYDRIDE and the FUMARIC ACID TECH GRADE acid anhydride;
B component is a monounsaturated dicarboxylic acid, a kind of in terephthalic acid and the hexanodioic acid;
Component C is saturated divalent alcohol, a kind of in butyleneglycol, Ucar 35 and the terepthaloyl moietie.
3. a kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester according to claim 2 is characterized in that, described solvent is a kind of in ETHYLE ACETATE, the YLENE, and described initiator is a Diisopropyl azodicarboxylate.
4. a kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester according to claim 2 is characterized in that, described catalyzer is a kind of in tetrabutyl titanate, Antimony Trioxide: 99.5Min, the dibutyl tin.
5. a kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester according to claim 2 is characterized in that described hard monomer is a TEB 3K.
6. a kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester according to claim 2 is characterized in that described soft monomer is a Bing Xisuandingzhi.
7. a kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester according to claim 2 is characterized in that described function monomer is a Rocryl 400.
8. a kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester according to claim 2 is characterized in that described monounsaturated dicarboxylic acid is a terephthalic acid.
9. a kind of preparation method who contains the acrylate pressure-sensitive adhesive of crystal type polyester according to claim 2 is characterized in that described saturated divalent alcohol is a butyleneglycol.
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| CN2012102777133A CN102775943A (en) | 2012-08-06 | 2012-08-06 | Acrylate pressure-sensitive adhesive containing crystalline polyester and preparation method thereof |
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| CN107903854A (en) * | 2017-12-25 | 2018-04-13 | 江苏景宏新材料科技有限公司 | A kind of acrylate pressure-sensitive adhesive containing unsaturated polyester (UP) and preparation method thereof |
| CN108047385A (en) * | 2017-12-14 | 2018-05-18 | 中国科学院深圳先进技术研究院 | A kind of pressure-sensitive resin of response type and preparation method thereof |
| CN111117502A (en) * | 2019-12-26 | 2020-05-08 | 安徽明讯新材料科技股份有限公司 | Improved protective film capable of being granulated together with glue and PET (polyethylene terephthalate) base material and manufacturing method thereof |
| CN114214011A (en) * | 2021-12-28 | 2022-03-22 | 西北工业大学宁波研究院 | Water-based adhesive and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047385A (en) * | 2017-12-14 | 2018-05-18 | 中国科学院深圳先进技术研究院 | A kind of pressure-sensitive resin of response type and preparation method thereof |
| CN108047385B (en) * | 2017-12-14 | 2020-07-24 | 中国科学院深圳先进技术研究院 | Reactive pressure-sensitive resin and preparation method thereof |
| CN107903854A (en) * | 2017-12-25 | 2018-04-13 | 江苏景宏新材料科技有限公司 | A kind of acrylate pressure-sensitive adhesive containing unsaturated polyester (UP) and preparation method thereof |
| CN111117502A (en) * | 2019-12-26 | 2020-05-08 | 安徽明讯新材料科技股份有限公司 | Improved protective film capable of being granulated together with glue and PET (polyethylene terephthalate) base material and manufacturing method thereof |
| CN114214011A (en) * | 2021-12-28 | 2022-03-22 | 西北工业大学宁波研究院 | Water-based adhesive and preparation method thereof |
| CN114214011B (en) * | 2021-12-28 | 2023-12-15 | 西北工业大学宁波研究院 | Water-based adhesive and preparation method thereof |
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Application publication date: 20121114 |